A Series of Dibenzofuran-Based n-Type Exciplex Host Partners Realizing High-Efficiency and Stable Deep-Red Phosphorescent OLEDs

Deep-red to near-infrared (NIR) OLEDs, which yield emission peak wavelengths beyond λ=660 nm, are applicable as unique light sources in plant growth or health monitoring systems. Compared with other visible-spectrum OLEDs, however, research in the field of deep-red OLEDs is not as advanced. In this work, three new types of dibenzofuran-based host materials are developed as n-type exciplex host partners. Combining these with the deep-red iridium complex bis(2,3-diphenylquinoxaline)iridium(dipivaloylmethane) ([(DPQ)₂Ir(dpm)]) and N,N′-di(naphalene-1-yl)-N,N′-diphenylbenzidine (α-NPD) as a p-type exciplex host partner, a highly efficient deep-red OLED can be realized with a maximum external quantum efficiency (η_ext,max) of over 16 % with Comission Internationale de l′Éclairge (CIE) coordinates of (0.71, 0.28). In addition, the effect of the doping concentration and the p/n ratio of the exciplex host on the efficiency and the lifetime of the OLEDs are investigated. Consequently, the optimized device exhibits a η_ext,max of over 15 % and a six-time longer lifetime operating at high brightness of 100 cd m⁻² compared with other state-of-the-art deep-red OLEDs.     

Synthesis of fluorene‐based hyperbranched polymers for solution‐processable blue,green, red,and white light‐emitting devices

For the purpose of making hyperbranched polymer (Hb‐Ps)‐based red, green, blue, and white polymer light‐emitting diodes (PLEDs), three Hb‐Ps Hb‐ terfluorene ( Hb‐TF ), Hb ‐4,7‐bis(9,9′‐dioctylfluoren‐2‐yl)‐2,1,3‐benzothiodiazole ( Hb‐BFBT ), and Hb‐ 4,7‐bis[(9,9′‐dioctylfluoren‐2‐yl)‐thien‐2‐yl]‐2,1,3‐benzothiodiazole ( Hb‐BFTBT ) were synthesized via [2+2+2] polycyclotrimerization of the corresponding diacetylene‐functionalized monomers. All the synthesized polymers showed excellent thermal stability with degradation temperature higher than 355 °C and glass transition temperatures higher than 50 °C. Photoluminance (PL) and electroluminance (EL) spectra of the polymers indicate that Hb‐TF , Hb‐BFBT , and Hb‐BFTBT are blue‐green, green, and red emitting materials. Maximum brightness of the double‐layer devices of Hb‐TF , Hb‐BFBT , and Hb‐BFTBT with the device configuration of indium tin oxide/poly(3,4‐ethylene dioxythiophene):poly(styrene sulfonate)/light‐emitting polymer/CsF/Al are 48, 42, and 29 cd/m²; the maximum luminance efficiency of the devices are 0.01, 0.02, and 0.01 cd/A. By using host–guest doped system, saturated red electrophosphorescent devices with a maximum luminance efficiency of 1.61 cd/A were obtained when Hb‐TF was used as a host material doped with Os(fptz)₂(PPh₂Me₂)₂ as a guest material. A maximum luminance efficiency of 3.39 cd/A of a red polymer light‐emitting device was also reached when Hb‐BFTBT was used as the guest in the PFO (Poly(9,9‐dioctylfluorene)) host layer. In addition, a series of efficient white devices were, which show low turn‐on voltage (3.5 V) with highest luminance efficiency of 4.98 cd/A, maximum brightness of 1185 cd/m², and the Commission Internationale de l'Eclairage (CIE) coordinates close to ideal white emission (0.33, 0.33), were prepared by using BFBT as auxiliary dopant. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Cascade hole transport in efficient green phosphorescent light‐emitting devices achieved by layer‐by‐layer solution deposition using photocrosslinkable‐conjugated polymers containing oxetane side‐chain moieties

A hole‐injection/transport bilayer structure on an indium tin oxide (ITO) layer was fabricated using two photocrosslinkable polymers with different molecular energy levels. Two photoreactive polymers were synthesized using 2,7‐(or 3,6‐)‐dibromo‐9‐(6‐((3‐methyloxetan‐3‐yl)methoxy)hexyl)‐9H‐carbazole) and 2,4‐dimethyl‐N,N‐bis(4‐ (4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)phenyl)aniline via a Suzuki coupling reaction. When the oxetane groups were photopolymerized in the presence of a cationic photoinitiator, the photocured film showed good solvent resistance and compatibility with a poly(N‐vinylcarbazole) (PVK)‐based emitting layer. Without the use of a conventional hole injection layer (HIL) of poly(3,4‐ethylenedioxythiophene)/(polystyrenesulfonate) (PEDOT:PSS), the resulting green light‐emitting device bearing PVK: 5‐4‐tert‐butylphenyl‐1,3,4‐oxadiazole (PBD):Ir(Cz‐ppy)3 exhibited a maximum external quantum efficiency of 9.69%; this corresponds to a luminous efficiency of 29.57 cd/A for the device K‐4 configuration ITO/POx‐I/POx‐II/PVK:PBD:Ir(Cz‐ppy)3/triazole/Alq3/LiF/Al. These values are much higher than those of PLEDs using conventional PEDOT:PSS as a single HIL. The significant improvement in device efficiency is the result of suppression of the hole injection/transport properties through double‐layered photocrosslinked‐conjugated polymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and characterization of electrophosphorescent jacketed conjugated polymers

A monomer containing bent side chains with oxadiazole unit was synthesized. And it was copolymerized with polyfluorene at different ratios. The photophysical and electrochemical properties of the copolymers were characterized. The results show that the introduction of the oxidiazole‐containing side chains into the polymer reduces the lowest unoccupied molecular orbital level. And the steric hindrance of the side groups can effectively suppress the aggregation of the polymer backbones. Electroluminescent devices were fabricated with a configuration of indium tin oxide (ITO)/poly(3,4‐ethylenedioxythiophene (PEDOT):PSS/Sample/Ca/Al. All of the devices emit blue light. The device of the copolymer PFOXD50 shows the best performance with the maximum luminance of 1033 cd/m² and the maximum current efficiency of 0.29 cd/A. Then a cyclometalated iridium complex monomer (ppy)₂Ir(BrPhPyBr) was copolymerized with PFOXD50 at different ratios. The devices with the same configuration emit orange light. The efficiency generally increases with the increasing Ir content. Among them, the device of the copolymer PFOXDIr7 shows the best performance with the maximum luminance of 846 cd/m² and the maximum current efficiency of 0.61 cd/A. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

发光二极管特性的实验研究

通过实验,对红、绿、蓝三种颜色的LED的发光稳定性、伏安特性和发光波长进行了研究。采用开启电压测量法和分光计测量法,研究了LED的发射波长,实验显示两种方法的结果是相符合的,说明开启电压法是可行的。     

Perdeuterated Conjugated Polymers for Ultralow-Frequency Magnetic Resonance of OLEDs

The formation of excitons in OLEDs is spin dependent and can be controlled by electron-paramagnetic resonance, affecting device resistance and electroluminescence yield. We explore electrically detected magnetic resonance in the regime of very low magnetic fields (<1 mT). A pronounced feature emerges at zero field in addition to the conventional spin- Zeeman resonance for which the Larmor frequency matches that of the incident radiation. By comparing a conventional π-conjugated polymer as the active material to a perdeuterated analogue, we demonstrate the interplay between the zero-field feature and local hyperfine fields. The zero-field peak results from a quasistatic magnetic-field effect of the RF radiation for periods comparable to the carrier-pair lifetime. Zeeman resonances are resolved down to 3.2 MHz, approximately twice the Larmor frequency of an electron in Earth's field. However, since reducing hyperfine fields sharpens the Zeeman peak at the cost of an increased zero-field peak, we suggest that this result may constitute a fundamental low-field limit of magnetic resonance in carrier-pair-based systems. OLEDs offer an alternative solid-state platform to investigate the radical-pair mechanism of magnetic-field effects in photochemical reactions, allowing models of biological magnetoreception to be tested by measuring spin decoherence directly in the time domain by pulsed experiments.     

Stable deep blue organic light emitting diodes with CIE of y < 0.10 based on quinazoline and carbazole units

Achieving stable deep blue organic light emitting diodes (OLEDs) with narrow full width at half maximum (FWHM) and color gamut in the range of the commission International de L’Eclairage (CIE) of y ≤ 0.10 is still challenging in display and lighting applications. In this investigation, three donor-acceptor (D-A) deep-blue emitters were designed and synthesized via integrating asymmetric quinazoline (PQ) acceptor with weak donating carbazole (Cz) donor. The effect of the position and number of Cz group in PQ unit are investigated, which is also first examples for systematic research about the effect of different position of asymmetric PQ as acceptor on deep OLEDs. Their bandgaps of 3.12∼3.19 eV and the singlet state energy levels of 3.12∼3.19 eV were found to be sufficiently large to achieve deep blue light. As expected, these emitters-based OLEDs exhibit deep blue emission with the maximum wavelength ≤ 450 nm and narrow FWHM ≈ 60 nm. Especially, a CIE of y = 0.080 was achieved for 4PQ-Cz-based OLED. Significantly, the deep blue electroluminescence (EL) spectra of these three emitters-based OLEDs are very stable and the corresponding CIE coordinates deviation (ΔCIE (x, y)) can be negligible under the applied voltage ranging from 5 V to 9 V.     

Manipulation of Phosphorescence Efficiency of Cyclometalated Iridium Complexes by Substituted o‐Carboranes

A series of [(C^N)₂Ir(acac)] complexes [{5‐(2‐R‐CB)ppy}₂Ir(acac)] ( 3 a – 3 g ; acac=acetylacetonate, CB=o‐carboran‐1‐yl, ppy=2‐phenylpyridine; R=H ( 3 a ), Me ( 3 b ), iPr ( 3 c ), iBu ( 3 d ), Ph ( 3 e ), CF₃C₆H₄ ( 3 f ), C₆F₅ ( 3 g )) with various 2‐R‐substituted o‐carboranes at the 5‐position in the phenyl ring of the ppy ligand were prepared. X‐ray diffraction studies revealed that the carboranyl C?C bond length increases with increasing steric and electron‐withdrawing effects from the 2‐R substituents. Although the absorption and emission wavelengths of the complexes are almost invariant to the change of 2‐R group, the phosphorescence quantum efficiency varies from highly emissive (Φ_PL≈0.80 for R=H, alkyl) to poorly emissive (R=aryl) depending on the 2‐R group and the polarity of the medium. Theoretical studies suggest that 1) the almost nonemissive nature of the 2‐aryl‐substituted complexes is mainly attributable to the large contribution to the LUMO in the S₁ excited state from an o‐carborane unit and 2) the variation in the C?C bond length between the S₀ and T₁ state structures increases with increasing steric (2‐alkyl) and electronic effects (2‐aryl) of the 2‐R substituent and the polarity of the solvent. The solution‐processed electroluminescence (EL) devices that incorporated 3 b and 3 d as emitters displayed higher performance than the device based on the parent [(ppy)₂Ir(acac)] complex. Along with the high phosphorescence efficiency, the bulkiness of the 2‐R‐o‐carborane unit is shown to play an important role in improving device performance.     

Novel panchromatic photopolymerizable matrices: N,N'‐dibutylquinacridone as an efficient and versatile photoinitiator

N,N'‐dibutylquinacridone (DBQA) is utilized here for the first time as a high‐performance panchromatic photoinitiator for the cationic polymerization (CP) of epoxides, the free radical polymerization (FRP) of acrylates, the thiol‐ene polymerization and the synthesis of interpenetrated polymer networks (epoxide/acrylate) under violet, blue, green and yellow lights (emitted from LED at 405 nm, 470 nm, 520 nm, or 594 nm, or laser diode at 532 nm). It confers a panchromatic character to the photopolymerizable matrices. Remarkably, the proposed DBQA based photoinitiating systems exhibit quite excellent efficiency (the final monomer conversion for multifunctional monomers at room temperature can reach 62% and 50% in CP and FRP, respectively) and appear as much more powerful than the camphorquinone or Eosin‐Y containing reference systems for visible light. For green light, DBQA is much more reactive than the literature reference (Eosin‐Y) and for blue light, a good reactivity is found compared with camphorquinone. The photochemical mechanisms are studied by molecular orbital calculations, steady state photolysis, fluorescence, cyclic voltammetry, laser flash photolysis, and electron spin resonance spin trapping techniques. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1719–1727     

Keto-coumarin scaffold for photoinitiators for 3D printing and photocomposites

The purposes of this paper are moving toward (a) the development of a new series of photoinitiators (PIs) which are based on the keto-coumarin (KC) core, (b) the introduction of light-emitting diodes (LEDs) as inexpensive and safe sources of irradiation, (c) the study of the photochemical mechanisms through which the new PIs react using different techniques such as Fourier transform infrared, UV–visible or fluorescence spectroscopy, and so on, (d) the use of such compounds (presenting good reactivity and excellent photopolymerization initiating abilities) for two specific and high added value applications: 3D printing (@405 nm) and preparation of thick glass fiber photocomposites with excellent depth of cure, and finally (e) the comparison of the performance of these KC derivatives versus other synthesized coumarin derivatives. In this study, six well-designed KC derivatives ( KC-C , KC-D , KC-E , KC-F , KC-G , and KC-H ) are examined as high-performance visible-light PIs for the cationic polymerization of epoxides as well as the free-radical polymerization of acrylates upon irradiation with LED@405 nm. Excellent polymerization rates are obtained using two different approaches: a photo-oxidation process in combination with an iodonium (Iod) salt and a photo-reduction process when associated with an amine (N-phenylglycine or ethyl 4-(dimethylamino)benzoate). High final reactive conversions were obtained. A full picture of the involved photochemical mechanisms is provided.